CN103502318A - Inorganic polysilazane, silica film-forming coating liquid containing same, and method for forming silica film - Google Patents

Inorganic polysilazane, silica film-forming coating liquid containing same, and method for forming silica film Download PDF

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CN103502318A
CN103502318A CN201280020940.6A CN201280020940A CN103502318A CN 103502318 A CN103502318 A CN 103502318A CN 201280020940 A CN201280020940 A CN 201280020940A CN 103502318 A CN103502318 A CN 103502318A
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inorganic polysilazane
silicon dioxide
polysilazane
dioxide film
coating fluid
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森田博
小林纯
横田洋大
降幡泰久
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Adeka Corp
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Asahi Denka Kogyo KK
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Abstract

The present invention provides: an inorganic polysilazane which does not contract much in a firing process in an oxidant such as water vapor and provides a silica film that is not easily cracked nor separated from a semiconductor substrate; and a silica film-forming coating liquid which contains the inorganic polysilazane. The present invention specifically provides: an inorganic polysilazane which has a value of A/(B + C) of 0.9-1.5 and a value of (A + B)/C of 4.2-50 when the peak area within the range from 4.75 ppm (inclusive) to 5.4 ppm (exclusive) is represented by A, the peak area within the range from 4.5 ppm (inclusive) to 4.75 ppm (exclusive) is represented by B, and the peak area within the range from 4.2 ppm (inclusive) to 4.5 ppm (exclusive) is represented by C in an 1H-NMR spectrum, while having a mass average molecular weight of 2,000-20,000 in terms of polystyrene; and a silica film-forming coating liquid which contains the inorganic polysilazane.

Description

Inorganic polysilazane, the silicon dioxide film that contains it form the formation method with coating fluid and silicon dioxide film
Technical field
The present invention relates to have specific formation inorganic polysilazane, contain this inorganic polysilazane and organic solvent and form by coating fluid and the formation method of having used its silicon dioxide film as the silicon dioxide film of neccessary composition.
Background technology
The silicon dioxide film that the silicon oxide of take is main component, due to good aspect insulativity, thermotolerance, wearability and solidity to corrosion, is widely used so conduct is coated with the insulating film of material and semiconductor device firmly.Along with the miniaturization of semiconductor device, wish can the landfill narrow gap insulating film material.The insulating film used in semiconductor device for example can pass through CVD(Chemical Vapor Deposition, chemical vapour deposition) method or coating method form.Coating method is good aspect cost and productivity, so take, to improve quality be purpose, studied various materials.
Polysilazane is with-SiH 2the macromolecular compound that-NH-is elementary cell, be coating method by less expensive method, can form that for narrow gap quality is also good take the silicon dioxide film that silicon oxide is main component.
As forming the method for silicon dioxide film with polysilazane, the known method with following operation: (1) use the drying process, (3) that by the solution coat of the dimethylbenzene of polysilazane or dibutyl ether etc., the painting process on semiconductor substrate etc., the semiconductor substrate that (2) will be coated with polysilazane etc. are heated to 150 ℃ of left and right and make the solvent evaporation such as spinner by this semiconductor substrate etc. under the existence of the oxygenants such as water vapor and the firing process burnt till under 230～900 ℃ of left and right (for example, with reference to patent documentation 1 and 2).Polysilazane is converted into silicon-dioxide by the firing process in water vapor.
In addition, in firing process, polysilazane is converted under the effect of the water vapor as oxygenant that the reaction of silicon-dioxide is known means (for example, with reference to non-patent literature 1) by following reaction formula (1) and reaction formula (2).
-(SiH 2-NH)-+2H 2O→-(SiO 2)-+NH 3+2H 2 (1)
(SiH 2-NH)-+2O 2→-(SiO 2)-+NH 3 (2)
In the formation of the silicon dioxide film that has used polysilazane, polysilazane is filmed and can be shunk in becoming the process of silicon dioxide film.In order to improve the reactivity that becomes silicon-dioxide from polysilazane, reduce the silanol group (Si-OH) of silica sphere simultaneously, improve insulativity, the firing process in preferably under high temperature more, carrying out water vapor, but burning till under high temperature can make this contraction also become large.When the shrinking percentage in the firing process in water vapor is higher, be full of cracks, silicon dioxide film the peeling off from semiconductor substrate of silicon dioxide film occur sometimes, particularly, in the interelement separate use by inorganic polysilazane narrower gap for the element spacing of landfill semiconductor device, and while at high temperature being burnt till, the problem that exists easy generation be full of cracks and peel off.From now on, the requirement that becomes narrower semiconductor device due to the interval to making semiconductor element, obtain so need to shrink the inorganic polysilazane suppressed.
Following content is disclosed in patent documentation 3: the SiH in molecule 2base is with respect to SiH 3the ratio of base be 2.5～8.4 and elemental ratio be Si:N:H=50～70 quality %:20～34 quality %:5～9 quality % polysilazane has good thermotolerance, wearability and chemical proofing, simultaneously the mulch film that surface hardness is higher can be formed, ceramic formation body, binding agent that particularly the ceramics forming sintered compact is used can be suitable as.But above-mentioned polysilazane is due to SiH 3the content of base is more, so the contraction in the firing process in water vapor is larger, when being burnt till more than 500 ℃, exists the problem of the be full of cracks of easy generation silicon dioxide film.
Disclose following content in patent documentation 4: the protective membrane of the UV-preventing glass that the following polysilazane of take is neccessary composition forms and coats on the UV-preventing layer on glass planar with composition; and heated in dry air; form thus the protective membrane that mechanical strength and chemical stability are good, described polysilazane 1in the peak area ratio of H-NMR spectrum, SiH 3with respect to SiH 1, SiH 2and SiH 3the ratio of sum be 0.13～0.45 and number-average molecular weight be 200～100000.
Following content is disclosed in patent documentation 5: 1in the peak area ratio of H-NMR spectrum, SiH 3with respect to SiH 1and SiH 2the ratio of sum is adjusted to interlayer dielectric that the inert organic solvents solution of 0.15～0.45 polysilazane forms and forms and have good storage stability and coating characteristics with coating fluid, simultaneously, can reproducibility form well that insulativity is high, densification and the good mulch film of surface shape.In addition, also disclose and can be substituted by trimethyl silyl adjusted by a part of active hydrogen by polysilazane, and used hexamethyldisilazane as adjusting agent.But, make hexamethyldisilazane reaction and contraction in the firing process of polysilazane in water vapor that obtain is larger, when being burnt till more than 500 ℃, exist the problem of the be full of cracks of easy generation silicon dioxide film.
Following content is disclosed in patent documentation 6: provide contraction in a kind of firing process in water vapor little and be difficult for occurring the silicon-dioxide mulch film be full of cracks and with the insulating film of peeling off of semiconductor substrate form with coating fluid, used this coating fluid insulating film with and the manufacture method of the compound of use, described insulating film forms and is characterised in that with coating fluid, and it contains: 1in H-NMR spectrum, from SiH 1base and SiH 2the peak area of 4.5～5.3ppm of base is with respect to from SiH 3inorganic polysilazane and organic solvent that the ratio of the peak area of 4.3～4.5ppm of base is 4.2～50.But, in order to reduce the residual carbon in silicon dioxide film, sometimes require to carry out high temperature and burn till, just require further to improve thermal contraction.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 7-223867 communique
Patent documentation 2: No. 6767641 communiques of U.S. Patent bulletin
Patent documentation 3: Japanese kokai publication hei 1-138108 communique
Patent documentation 4: Japanese kokai publication hei 5-311120 communique
Patent documentation 5: Japanese kokai publication hei 10-140087 communique
Patent documentation 6: TOHKEMY 2011-79917 communique
Non-patent literature
Non-patent literature 1: electronic material, in December, 1994, p50
Summary of the invention
The problem to be solved in the present invention
Therefore, the purpose of this invention is to provide contraction in a kind of firing process in the oxygenants such as water vapor little and be difficult for occurring the be full of cracks of silicon dioxide film and form and use coating fluid with the inorganic polysilazane of peeling off of semiconductor substrate and the silicon dioxide film that contains inorganic polysilazane.
The means of dealing with problems
The present inventor finds, the molecular weight of inorganic polysilazane, SiH 3the contraction when silicon-dioxide in base and the side chain stretched out from nitrogen-atoms and firing process transforms has relation, thereby has completed the present invention.
That is, the invention provides a kind of inorganic polysilazane, wherein, 1in H-NMR spectrum, to more than 4.75ppm and lower than the peak area of the scope of 5.4ppm, be set as A, to more than 4.5ppm and lower than the peak area of the scope of 4.75ppm, be set as B, when more than 4.2ppm and lower than the peak area of the scope of 4.5ppm, being set as C, A/(B+C) value is 0.9～1.5, (A+B) value of/C is 4.2～50, and the matter average molecular weight obtained according to the polystyrene conversion value is 2000～20000.
In addition, the invention provides a kind of silicon dioxide film and form and use coating fluid, it contains above-mentioned inorganic polysilazane and organic solvent as neccessary composition.
In addition, the invention provides a kind of formation method of silicon dioxide film, it is characterized in that, above-mentioned silicon dioxide film is formed and coats on matrix with coating fluid, make this coating fluid and oxidant reaction, thereby form silicon dioxide film.
The effect of invention
According to the present invention, can provide the contraction in a kind of firing process under the existence of oxygenant little polysilazane.
The accompanying drawing explanation
Fig. 1 is the figure of the infrared spectra of the inorganic polysilazane that describes of the method for calculation for the NH/SiH dulling luminosity ratio to the present invention.
Fig. 2 is that the silicon dioxide film of manufacturing in embodiment 1 forms with coating fluid No.1 1the figure of H-NMR spectrum.
Fig. 3 is that the silicon dioxide film of manufacturing in embodiment 2 forms with coating fluid No.2 1the figure of H-NMR spectrum.
Fig. 4 is that the silicon dioxide film of manufacturing in embodiment 3 forms with coating fluid No.3 1the figure of H-NMR spectrum.
Embodiment
Below, according to preferred embodiment the present invention is described in detail.
Inorganic polysilazane of the present invention is characterised in that, 1in H-NMR spectrum, to more than 4.75ppm and lower than the peak area of the scope of 5.4ppm, be set as A, to more than 4.5ppm and lower than the peak area of the scope of 4.75ppm, be set as B, when more than 4.2ppm and lower than the peak area of the scope of 4.5ppm, being set as C, A/(B+C) value is 0.9～1.5, (A+B) value of/C is 4.2～50, and the matter average molecular weight obtained according to the polystyrene conversion value is 2000～20000.
Inorganic polysilazane refers to-SiH 2-NH-is elementary cell, and does not contain the polysilazane of organic group in its structure.In general, be not the polymkeric substance of straight chain, but the polymkeric substance that contains branched structure, crosslinking structure, ring texture exist the side chain stretched out from Siliciumatom, the side chain stretched out from nitrogen molecule in described branched structure.As the silicon unit, there is the unit of following formula S-1～S-4, as the nitrogen unit, there is the unit of following formula N-1～N-3.
Figure BDA0000403834320000051
At inorganic polysilazane 1in H-NMR spectrum, from the absorption spectrum of the hydrogen atom with silicon atom bonding, can obtain the relative amount of the said units inorganic polysilazane.The hydrogen atom of cell S-1 has absorption more than 4.2ppm and lower than the scope of 4.5ppm.The hydrogen atom of cell S-2 and S-3 has absorption more than 4.5ppm and lower than the scope of 5.4ppm, and the absorption of the hydrogen atom of cell S-3 is present in downfield (high frequency) zone of absorption of the hydrogen atom of relative cell S-2.In addition, downfield (high frequency) zone of absorption that also is present in the hydrogen atom of silicon atom bonding contained in relative and unit N-2 with the absorption of the hydrogen atom of silicon atom bonding contained in unit N-3.
When cell S-1 is included in unit N-3, the absorption of the hydrogen atom of cell S-1 is present in the downfield zone that relative cell S-1 is included in the situation in unit N-2.These absorb wide and the ground that overlaps is determined.4.2ppm in the present invention is above and lower than be equivalent in inorganic polysilazane-SiH of the peak area C of the scope of 4.5ppm 3the number of hydrogen atoms of base.
1in H-NMR spectrum, 4.5ppm above and lower than the absorption of the scope of 5.4ppm from the downfield side, be contained SiH in SiH, unit N-3 contained in unit N-3 2, contained SiH in contained SiH and N-2 in unit N-2 2absorption.
That is, the downfield side is the absorption with the hydrogen atom of the silicon atom bonding of unit N-3, the absorption of the hydrogen atom of the silicon atom bonding of Ce Shiyu unit, upfield N-2.These peak width and the ground that overlaps are determined.The large percentage of the absorption area of downfield side means that the ratio of unit N-3 is more, and the large percentage of the absorption area of upfield side means that the ratio of unit N-2 is more.
Here, when the absorption of this scope is divided with 4.75ppm, can say: unit N-3 exist number to increase the time, 4.75ppm in the present invention is above and become large lower than the peak area A of the scope of 5.4ppm, unit N-2 exist number to increase the time, 4.5ppm is above and become large lower than the peak area B of the scope of 4.75ppm.
That is, the A/(B+C in the present invention) be the index that has number of the unit N-3 in inorganic polysilazane, (A+B)/C is the SiH in inorganic polysilazane 3the index that has number of base.
In inorganic polysilazane of the present invention, as the A/(B+C of the index that has number of unit N-3) value be 0.9～1.5, be preferably 1.0～1.4.
A/(B+C) if value be less than 0.9, what can't obtain in firing process shrinking percentage while being converted into silicon-dioxide reduces effect fully.In addition, if this value is greater than 1.5, be also same.
Be greater than for the value of (A+B)/C the reason that 0.9 o'clock shrinking percentage reduces, we investigate and are: when unit N-3 is converted into silicon-dioxide, because 1 dinitrogen is replaced into 1.5 molecular oxygens, so the cause that the shared volume in unit increases.
For A/(B+C) value be greater than the reason that reduces effect that can't obtain shrinking percentage at 1.5 o'clock, we investigate: if unit N-3 increases, when inorganic polysilazane transforms to silicon-dioxide, needed amino molecule tails off, consequently, the ratio that Si-N key in inorganic polysilazane is converted into the Si-O key diminishes, the unconverted part of the polysilazane for silicon-dioxide is lost as exhaust, and the effect that the contraction of unit N-3 suppresses can be eliminated.
The value of (A+B)/C in inorganic polysilazane of the present invention is 4.2～50, is preferably 4.5～20.
(A+B) if/value of C is less than 4.2, it is large that the shrinking percentage while in firing process, being converted into silicon-dioxide becomes.In addition, this value is greater than 50 inorganic polysilazane and is difficult to manufacture.(A+B) the less SiH that means of the value of/C 3base is more, SiH 3base is decomposed when silicon-dioxide transforms, as the exhaust of single silane and lose.Be greater than 50 inorganic polysilazane for the value of (A+B)/C and be difficult to the reason of manufacturing, we investigate and to be: due to when the reacting of ammonia and halogenated silanes, the homogenizing reaction occurs not in part halogenated silanes before the polymerization physical reaction, the cause changed with the quantity of the hydrogen atom of Siliciumatom adjacency.
For the molecular weight of inorganic polysilazane of the present invention, the weight-average molecular weight obtained according to the polystyrene conversion value is 2000～20000, is preferably 3000～10000.
If weight-average molecular weight is less than 2000, in the drying process and firing process when silicon dioxide film forms, the exhaust produced from filming increases, and causes the decline of thickness of silicon dioxide film or the generation of be full of cracks.If be greater than 20000, the landfill deterioration of the pattern that fine pattern and long-width ratio are larger, be difficult to form good silicon dioxide film.
In addition, when the low molecular weight compositions in inorganic polysilazane of the present invention is too much, in drying process and firing process, the volatile matter or the sublimate that from filming, produce increase, likely cause the decline of thickness of silicon dioxide film or the generation of be full of cracks, so the ratio that the matter average molecular weight in inorganic polysilazane of the present invention is the composition below 800 is preferably below 40%, more preferably below 30%.
In addition, in the present invention, the matter average molecular weight refers to that take tetrahydrofuran (THF) (THF) is solvent, uses the matter average molecular weight of the polystyrene conversion of differential refraction rate detector (RI detector) while carrying out gpc analysis.In addition, the ratio that matter average molecular weight in inorganic polysilazane of the present invention is the composition below 800 refers to, the peak area ratio of the inorganic polysilazane when carrying out gpc analysis, the matter average molecular weight of polystyrene conversion is polysilazane amount below 800 ratio with respect to whole polysilazane amount.
In the infrared spectra of inorganic polysilazane of the present invention, from the absorption of Si-H key, be positioned at 2050～2400cm -1, from the absorption of N-H key, be positioned at 3300～3450cm -1.Therefore, due to 2050～2400cm -1absorbancy corresponding to the number of the hydrogen atom with silicon atom bonding, 3300～3450cm -1absorbancy corresponding to the number of the hydrogen atom with nitrogen atom bonding, so 3300～3450cm in infrared spectra -1the maximum absorbance of scope with respect to 2050～2400cm -1the ratio of maximum absorbance of scope become with the number of hydrogen atoms of nitrogen atom bonding/with the index of the number of hydrogen atoms of silicon atom bonding.In the present invention, below by this than being called the NH/SiH dulling luminosity ratio.
In inorganic polysilazane of the present invention, if the NH/SiH dulling luminosity ratio is less than 0.01, the storage stability of inorganic polysilazane of the present invention likely becomes bad, if be greater than 0.20, contraction while burning till the silicon-dioxide conversion caused likely becomes large, so the NH/SiH dulling luminosity ratio is preferably 0.01～0.20, more preferably 0.10～0.20.
The infrared spectra of the inorganic polysilazane in the present invention can be measured by any method in transmission method and reflection method.While measuring by transmission method, can be by 2050～2400cm -1with 3300～3450cm -1place without the inorganic polysilazane of coating on the test film of the Interference absorb of infrared spectra, then measures infrared spectra and obtains in fact.While measuring by reflection method, also can be with measuring with the same test film of transmission method, but compare with transmission method, S/N is than variation likely.Method easy and that reproducibility is good is for example following method: using silicon wafer that two sides ground as matrix, with spinner, be coated with and make its drying, measured by seeing through dried inorganic polysilazane.
When the thickness of the inorganic polysilazane formed is 300～1000nm, can precision obtain well the NH/SiH dulling luminosity ratio on above-mentioned matrix.The mensuration of relevant infrared spectra, because the data processing after measuring is easy to cause, preferably used fourier transformation type infrared spectrometer (FT-IR).
NH/SiH dulling luminosity ratio in the present invention is the value that the spectrogram by the infrared spectra of inorganic polysilazane obtains by peak intensity method.For example,, in Fig. 1, by 2050cm -1, 2400cm -1, 3300cm -1and 3450cm -1point place, on the absorbancy curve is set as respectively an A, some B, some E and some F, by 2050～2400cm -1scope and 3300～3450cm -1scope in the wave number of absorbancy while reaching maximum, point on the absorbancy curve be set as respectively a C and some G, will be from a C to reference line the vertical line of (line that absorbancy is 0 o'clock, blank) and the intersection point of line AB be set as a D, when the intersection point of the vertical line from a G to reference line and line EF is set as to some H, the NH/SiH dulling luminosity ratio is equivalent to the ratio of line segment GH with respect to line segment CD.That is, NH/SiH dulling luminosity ratio of the present invention is in the spectrogram of the infrared spectra of inorganic polysilazane, to connect 3300cm -1point and the 3450cm of absorbancy -1the line of point of absorbancy as 3300～3450cm of baseline -1the absorbancy maximum value with respect to connect 2050cm -1point and the 2400cm of absorbancy -1the line of point of absorbancy as 2050～2400cm of baseline -1the peaked ratio of absorbancy.
In addition, usually, inorganic polysilazane is at 2050～2400cm -1the scope internal absorbance to reach maximum be at 2166cm -1near, at 3300～3450cm -1the scope internal absorbance to reach maximum be at 3377cm -1near.
The specific refractory power that inorganic polysilazane of the present invention is the 633nm place at wavelength is less than at 1.550 o'clock, contraction while burning till the silicon-dioxide conversion caused likely becomes large, be greater than at 1.650 o'clock, silicon dioxide film of the present invention forms and likely becomes bad with the storage stability of coating fluid, so the specific refractory power that wavelength is the 633nm place is preferably 1.550～1.650, more preferably 1.560～1.640, most preferably be 1.570～1.630.
The measuring method of above-mentioned specific refractory power is such as using the methods such as spin-coating method, dip coating, scraper for coating method, rolling method that inorganic polysilazane or dissolving or the composition that is dispersed with inorganic polysilazane are coated on matrix, then dry, form inorganic polysilazanes film and measured.The difference of the dry thickness according to inorganic polysilazanes film and difference, but while being 500～1000nm, preferably under 150 ℃, heating, more than 1 minute, is more preferably heated about 3 minutes under 150 ℃.In the situation of nitrogen content identical inorganic polysilazane with respect to the ratio of silicone content, hydrogen richness in the higher inorganic polysilazane of specific refractory power is less, there is a large amount of ring structures in molecule, it is believed that, this can form and exert an influence with the storage stability of coating fluid and the contraction in the firing process in water vapor silicon dioxide film.
The manufacture method of inorganic polysilazane of the present invention is not particularly limited, and the manufacture method manufacture that is suitable for or applies well-known inorganic polysilazane gets final product.For example, can make halogenated silanes compound and ammonia direct reaction, also can make the affixtures such as alkali and the addition of halogenated silanes compound and form to add adult, then make this add adult and ammonia react.Via this manufacture method that adds adult and manufacture inorganic polysilazane such as being disclosed in Japanese kokai publication sho 60-145903 communique, Japanese kokai publication sho 61-174108 communique etc.
As the manufacture method of inorganic polysilazane of the present invention, from controlling the viewpoint of reaction, preferably make halogenated silanes compound and alkali reaction and, after forming and adding adult, make this add the method for adult and ammonia react.
After forming making halogenated silanes compound and alkali reaction and adding adult, make in the manufacture method of this inorganic polysilazane that adds adult and ammonia react, this adds adult and carries out at the temperature of-50～20 ℃ with reacting normally of ammonia, preferably at the temperature of-10～15 ℃, carries out.
The halogenated silanes compound used in raw material as inorganic polysilazane of the present invention, can list the dihalide halosilanes compounds such as dichlorosilane, two bromo-silicanes, chlorine bromo-silicane; Trihalosilane compound, tetrachloro silicane, the tetrabromo silane such as trichlorosilane, tribromosilane, dichloro bromo-silicane, chlorine two bromo-silicanes, as halogenated silanes, the chlorosilane class is due to cheap and preferred.The halogenated silanes compound can only be used a kind of, also can more than two kinds, be used in combination.Used the inorganic polysilazane of dihalide halosilanes compound to have advantages of that film-forming properties is good, contraction while having used the inorganic polysilazane of trihalosilane compound to have advantages of sintering is less, while manufacturing inorganic polysilazane of the present invention, preferably use dihalide halosilanes compound, trihalosilane compound or dihalide halosilanes compound and trihalosilane compound are used.
During by dihalide halosilanes compound and the use of trihalosilane compound, viewpoint from the quantity of control unit S-2, its ratio is, with respect to 1 mole of dihalide halosilanes compound, the trihalosilane compound is preferably 0.01～2 mole, more preferably 0.03～1 mole, most preferably be 0.05～0.5 mole.
In addition, for as to be used to form the affixture that adds adult be alkali, so long as except with the halogenated silanes compound formation adds reacting of adult, for inactive alkali gets final product.As this alkali, can list tertiary amines such as Trimethylamine, triethylamine, tributylamine, xylidine; The pyridines such as pyridine, picoline, from the viewpoint of the easiness of the easiness of industrial acquisition and processing, preferably pyridine and picoline, more preferably pyridine.The amount of the alkali used is to get final product more than 1 times mole with respect to the halogen atom of halogenated silanes compound, but is preferably more than 1.1 times moles, insufficient with the formation of avoiding adding adult.
In the manufacture method of inorganic polysilazane of the present invention, form above-mentionedly while adding adult, the mobility of reaction system descends, so add the formation reaction of adult, preferably in organic solvent, carries out.This solvent can be used the organic solvent do not reacted with inorganic polysilazane.For example can list pentane, hexane, heptane, octane, pure isooctane (also referred to as octane-iso), isononane, 2,2,4,6, the saturated chain hydrocarbon compounds such as 6-five methylheptane (also referred to as Permethyl 99A.); The saturated cyclic hydrocarbon compounds such as pentamethylene, hexanaphthene, methylcyclohexane, ethylcyclohexane, naphthane; The aromatic hydrocarbon compounds such as benzene,toluene,xylene, ethylbenzene, cumene, pseudocumol, tetraline; Anaesthetie Ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ether, diisobutyl ether, t-butyl methyl ether, tetrahydrofuran (THF), diox, 1, the ether compounds such as 2-glycol dimethyl ether etc.
In addition, as the alternative reaction solvent of organic solvent, also can use the excessive alkali as affixture, using excessive alkali as solvent.Particularly preferably be: using pyridine as affixture, even finish also with this degree that keeps mobility, excessively to use pyridine according to forming reaction, and do not use other organic solvent.Now, the usage quantity of pyridine is preferably 3～30 times moles with respect to the halogenated silanes compound, and more preferably 4～25 times moles, more preferably 5～20 times moles.In addition, in order to prevent descending because formation adds the mobility that adult causes, can organic solvent, affixture, contain organic solvent and affixture mixed solvent in separately add halogenated silanes compound and ammonia, also can add continuously simultaneously.
In the manufacture method via adding adult, the usage quantity of ammonia is on stoichiometry, with respect to the halogen atom of the halogenated silanes compound used in reaction, for (more than 1 times mole) more than waiting mole, get final product, but adequacy and the economy of reaction have been considered, the usage quantity of ammonia is preferably 1.0～3.0 times moles with respect to the halogen atom of the halogenated silanes compound used in reaction, more preferably 1.1～2.5 times moles, most preferably be 1.2～2.0 times moles.
After ammonia react, remove as required superfluous ammonia, by halo ammonium filtration by generation etc., remove.Then, as required, can carry out solvent exchange etc. by known method and become desired organic solvent.
In addition, after inorganic polysilazane of the present invention also can or be removed before removing the salt of generation, make SiH base in inorganic polysilazane molecule and NH radical reaction and generate the Si-N key, thereby carry out ring-type, by intermolecular reaction, carry out polymer quantification etc. by intramolecular reaction, thus, also can seek SiH 3the minimizing that the increase of the minimizing of base, matter average molecular weight, matter average molecular weight are the composition below 800, the increase of NH/SiH dulling luminosity ratio, the adjustment such as increase of specific refractory power.As the SiH base that makes inorganic polysilazane and NH radical reaction and generate the method for Si-N key, such as can list the method (for example, with reference to Japanese kokai publication hei 1-138108 communique) heated in the basic solvents such as pyridine, picoline; The method (for example, with reference to Japanese kokai publication sho 60-226890 communique) of using alkalimetal hydride, alkali metal alkoxide, anhydrous alkali metal hydroxides etc. to contain alkali-metal basic catalyst; The method (for example, with reference to the flat 5-170914 communique of Japanese Unexamined Patent Application Publication) that the quaternary ammonium compounds such as Tetramethylammonium hydroxide of take are catalyzer; Use the method (such as with reference to JP table 2003-514822 communique) of the acid catalysts such as ammonium nitrate, ammonium acetate etc., the method heated in the affixture preferably used in reaction or the solvent that contains this affixture.
Use while via the method that adds adult, manufacturing inorganic polysilazane, for example, for example, because affixture (pyridine) after adding adult (dichlorosilane and pyridine) and ammonia react is free, so free affixture can be used as basic solvent.Therefore, after manufacturing inorganic polysilazane via adding adult, heated as solvent by the affixture using free, just can make the SiH base of inorganic polysilazane and NH radical reaction and generate the Si-N key, the viewpoint of the simplification of this effective utilization from raw material and manufacturing process is preferred.
It is to contain above-mentioned of the present invention inorganic polysilazane and organic solvent as the composition of neccessary composition that silicon dioxide film of the present invention forms with coating fluid, is modulated into the concentration of easily coating on matrix.
Relevant silicon dioxide film of the present invention forms with the organic solvent used in coating fluid, so long as can, because react the organic solvent that goes bad or react of this degree that causes damaging coating with inorganic polysilazane, just not be not particularly limited.Hydroxyl, aldehyde radical, ketone group, carboxyl, ester group etc. are owing to inorganic polysilazane, having high reactivity, so preferably do not contain the organic solvent of these groups.Form the preferred organic solvent with coating fluid as silicon dioxide film of the present invention, for example can list pentane, hexane, heptane, octane, 2,2,4-trimethylpentane (also referred to as octane-iso), isononane, 2,2, the saturated chain hydrocarbon compounds such as 4,6,6-five methylheptane (also referred to as Permethyl 99A.); The saturated cyclic hydrocarbon compounds such as pentamethylene, hexanaphthene, methylcyclohexane, naphthane; The aromatic hydrocarbon compounds such as benzene,toluene,xylene, ethylbenzene, cumene, pseudocumol, tetraline; Anaesthetie Ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ether, diisobutyl ether, t-butyl methyl ether, tetrahydrofuran (THF), diox, 1, the ether compounds such as 2-glycol dimethyl ether etc., wherein, due to the good cause of coating, preferred dimethylbenzene, dibutyl ether, due to the good cause of storage stability, more preferably dibutyl ether.Organic solvent can only be used a kind of, but also can be used in combination more than two kinds due to the purposes such as adjustment of velocity of evaporation.
For ether compound, as the by product of its raw material, manufacturing process, the deteriorated product in preservation, sometimes contain alkylol cpd, aldehyde cpd, ketone compound, carboxylic acid cpd, ester cpds etc.Silicon dioxide film of the present invention forms in the organic solvent with coating fluid while containing above-claimed cpd, it is large that contraction in firing process likely becomes, so with before inorganic polysilazane mixes, preferably the total content of above-mentioned alkylol cpd, aldehyde cpd, ketone compound, carboxylic acid cpd and ester cpds being set in advance in respect to dibutyl ether is below 0.1 quality %, more preferably, below 0.05 quality %, most preferably be below 0.01 quality %.
When silicon dioxide film formation of the present invention is too low with the content of the inorganic polysilazane in coating fluid, the film-forming properties of silicon dioxide film becomes insufficient, when too high, silicon dioxide film of the present invention forms and becomes insufficient with the storage stability of coating fluid, likely produce jello, so the content of inorganic polysilazane is preferably 1～40 quality %, more preferably 3～35 quality %, most preferably be 5～30 quality %.
Relevant silicon dioxide film of the present invention forms uses coating fluid; as mainly this coating fluid being coated on matrix (subject material); and make coating fluid and oxidant reaction and the silicon dioxide film that forms; can be for use the purposes of inorganic polysilazane in the past always; such as the insulating film of semiconductor device, the protective membrane of flat-panel monitor, the antireflection film of optical correlation goods etc., particularly can be suitable for the insulating film of semiconductor device.
For example in the situation that form the insulating film of semiconductor device, preferably comprise the manufacture method of following operation: silicon-dioxide of the present invention is formed to coat subject material (matrix) with coating fluid upper, and form the painting process of filming; Remove the drying process of organic solvent from film, burnt till in water vapor and form the firing process of silicon dioxide film.
While coating on subject material by silicon dioxide film formation of the present invention with coating fluid, be not particularly limited, the coating processes such as spray method, spin-coating method, dip coating, rolling method, flow coat method, silk screen print method, hectographic printing method all can be used, but owing to can forming the cause that thickness is thinner and film uniformly, preferred spin-coating method.
The drying temperature of drying process and time is according to the difference of used organic solvent and the thickness of filming and difference, but preferably 80～200 ℃, more preferably under 120～170 ℃, heat 1～30 minute, more preferably heat 2～10 minutes.Dry atmosphere can be any in oxygen, in air, in inactive gas.In addition, under the water vapour atmosphere that firing process is 20～100% in relative humidity, the temperature of 200～1200 ℃ is applicable scope.When firing temperature is low, reaction likely can not fully be carried out, simultaneously, the remaining decline that likely causes insulativity of silanol group, when firing temperature is higher, there is the problem of manufacturing cost, so the temperature of burning till under water vapour atmosphere is preferably 300～1000 ℃, more preferably 700～900 ℃.While burning till, can at the temperature more than 700 ℃, with 1 stage, be burnt till, can be also 200～500 ℃, be preferably under 300～450 ℃ and burn till 30～60 minutes after, 450～1200 ℃, be preferably 600～1000 ℃, the burning till of 2 stages of more preferably being burnt till under 700～900 ℃.Because the contraction of silicon dioxide film is less, be difficult for occurring the cause of be full of cracks, preferably 2 stages burns till.In addition, can be also 200～500 ℃, be preferably under 350～450 ℃ and burn till 30～60 minutes after, impregnated in the easy fired method (for example, with reference to Japanese kokai publication hei 7-223867 communique) in the distilled water of 20～80 ℃, but in the easy fired method, because the remaining meeting of silanol group causes the decline of insulativity, so preferably heat about 5～60 minutes under 700～900 ℃ in air after easy fired.
Embodiment
Below, specifically describe the present invention by embodiment, but they not delimit the scope of the invention.In addition, " part " in embodiment and " % " are based on quality.In addition, the purity of the dibutyl ether that solvent is used is 99.99%, and the total content of alkylol cpd, aldehyde cpd, ketone compound, carboxylic acid cpd and ester cpds is below 0.01%.
[embodiment 1]
In the glass of the 3000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 2310g(29.2 mole in nitrogen atmosphere), stir on one side, on one side by trichlorosilane 48.6g(0.36 mole) and dichlorosilane 82.6g(0.82 mole) with 1 hour, drip respectively, it is carried out coolingly so that temperature of reaction is 0～5 ℃ simultaneously, generate pyridine and add adult.Cooling not make temperature of reaction surpass the mode of 10 ℃ on one side, with 3 hour from ingress pipe import ammonia 78.9g(4.64 mole on one side), when being blown into nitrogen, then carry out stirring in 1.5 hours under 10 ℃, make to have reacted.After this reaction solution is heated to 10 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then solvent is changed to dibutyl ether from pyridinium crosslink.After the solution obtained is heated to 6 hours under 120 ℃, the PTFE that is 0.1 μ m with filtration diameter filter cartridge type filter processed is filtered, and obtains the silicon dioxide film formation coating fluid No.1 that inorganic polysilazane content is 11.3%.
[embodiment 2]
In the glass of the 3000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 2310g(29.2 mole in nitrogen atmosphere), stir on one side, on one side by trichlorosilane 50.4g(0.37 mole) and dichlorosilane 82.9g(0.82 mole) with 1 hour, drip respectively, it is carried out coolingly so that temperature of reaction is-10～0 ℃ simultaneously, generate pyridine and add adult.Cooling not make temperature of reaction surpass the mode of 5 ℃ on one side, with 3 hour from ingress pipe import ammonia 78.9g(4.61 mole on one side), when being blown into nitrogen, then carry out stirring in 1.5 hours under 10 ℃, make to have reacted.After this reaction solution is heated to 10 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then solvent is changed to dibutyl ether from pyridinium crosslink.After the solution obtained is heated to 6 hours under 120 ℃, the PTFE that is 0.1 μ m with filtration diameter filter cartridge type filter processed is filtered, and obtains the silicon dioxide film formation coating fluid No.2 that inorganic polysilazane content is 18.7%.
[embodiment 3]
In the glass of the 3000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 2411g(30.5 mole in nitrogen atmosphere), stir on one side, on one side by trichlorosilane 69.8g(0.52 mole) and dichlorosilane 51.3g(0.51 mole) with 1 hour, drip respectively, it is carried out coolingly so that temperature of reaction is-10～0 ℃ simultaneously, generate pyridine and add adult.Imported ammonia 74.4g(4.35 mole with 3 hours from ingress pipe under the temperature of reaction of-10～0 ℃), when being blown into nitrogen, then under 10 ℃, carry out stirring in 1.5 hours, make to have reacted.After this reaction solution is heated to 10 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then solvent is changed to dibutyl ether from pyridinium crosslink.After the solution obtained is heated to 6 hours under 120 ℃, the PTFE that is 0.1 μ m with filtration diameter filter cartridge type filter processed is filtered, and obtains the silicon dioxide film formation coating fluid No.3 that inorganic polysilazane content is 9.64%.
[comparative example 1]
In the glass of the 3000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 1646g(20.8 mole in nitrogen atmosphere), stir on one side, imported dichlorosilane 310g(3.1 mole with 1 hour from ingress pipe on one side under the temperature of reaction of 0～5 ℃), the pyridine that generates dichlorosilane adds adult.Imported ammonia 180g(10.6 mole with 1 hour from ingress pipe under the temperature of reaction of 0～5 ℃), then under 10 ℃, carry out stirring in 1.5 hours, make to have reacted.After this reaction solution is heated to 10 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then solvent is changed to dibutyl ether from pyridinium crosslink.The PTFE filter cartridge type filter processed that is 0.1 μ m with the filtration diameter under nitrogen atmosphere by the solution that obtains is filtered, and to obtain inorganic polysilazane content be 19.0% relatively uses coating fluid 1.
[comparative example 2]
In the glass of the 3000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 2248g(28.4 mole in nitrogen atmosphere), stir on one side, on one side by dichlorosilane 191.0g(1.89 mole) and ammonia 113.0g(6.65 mole) with 3 hours, import respectively, it is carried out cooling so that temperature of reaction is 0～5 ℃ simultaneously, when being blown into nitrogen, then carry out stirring in 1.5 hours under 10 ℃, make to have reacted.After this reaction solution is heated to 10 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then solvent is changed to dibutyl ether from pyridinium crosslink.After the solution obtained is heated to 6 hours under 120 ℃, the PTFE that is 0.1 μ m with filtration diameter filter cartridge type filter processed is filtered, and to obtain inorganic polysilazane content be 19.2% relatively uses coating fluid 2.
[comparative example 3]
In the glass of the 3000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 2044g(25.8 mole in nitrogen atmosphere), stir on one side, on one side by dichlorosilane 174.0g(1.72 mole) and ammonia 103.0g(6.06 mole) with 3 hours, import respectively, it is carried out cooling so that temperature of reaction is 0～5 ℃ simultaneously, when being blown into nitrogen, then carry out stirring in 1.5 hours under 10 ℃, make to have reacted.After this reaction solution is heated to 10 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then solvent is changed to dibutyl ether from pyridinium crosslink.After the solution obtained is heated to 6 hours under 120 ℃, the PTFE that is 0.1 μ m with filtration diameter filter cartridge type filter processed is filtered, and to obtain inorganic polysilazane content be 19.3% relatively uses coating fluid 3.
[comparative example 4]
In the glass of the 3000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 2303g(29.1 mole in nitrogen atmosphere), stir on one side, on one side by dichlorosilane 280.0g(2.77 mole) and ammonia 165.0g(9.71 mole) with 4 hours, import respectively, it is carried out cooling so that temperature of reaction is-10～0 ℃ simultaneously, when being blown into nitrogen, then carry out stirring in 1.5 hours under 0 ℃, make to have reacted.After this reaction solution is heated to 10 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then solvent is changed to dibutyl ether from pyridinium crosslink.After the solution obtained is heated to 6 hours under 120 ℃, the PTFE that is 0.1 μ m with filtration diameter filter cartridge type filter processed is filtered, and to obtain inorganic polysilazane content be 19.0% relatively uses coating fluid 4.
[comparative example 5]
In the glass of the 3000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 2044g(25.8 mole in nitrogen atmosphere), stir on one side, on one side by dichlorosilane 325.7g(3.22 mole) and ammonia 192.1g(11.3 mole) with 2 hours, import respectively, it is carried out cooling so that temperature of reaction is-10～0 ℃ simultaneously, when being blown into nitrogen, then carry out stirring in 1.5 hours under 0 ℃, make to have reacted.After this reaction solution is heated to 10 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then solvent is changed to dibutyl ether from pyridinium crosslink.After the solution obtained is heated to 6 hours under 120 ℃, the PTFE that is 0.1 μ m with filtration diameter filter cartridge type filter processed is filtered, and to obtain inorganic polysilazane content be 19.2% relatively uses coating fluid 5.
[comparative example 6]
In the glass of the 3000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 2044g(25.8 mole in nitrogen atmosphere), stir on one side, on one side by dichlorosilane 260.6g(2.58 mole) and ammonia 131.6g(7.74 mole) with 1.5 hours, import respectively, it is carried out cooling so that temperature of reaction is-10～0 ℃ simultaneously, when being blown into nitrogen, then carry out stirring in 1.5 hours under 0 ℃, make to have reacted.After this reaction solution is heated to 10 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then solvent is changed to dibutyl ether from pyridinium crosslink.After the solution obtained is heated to 6 hours under 120 ℃, the PTFE that is 0.1 μ m with filtration diameter filter cartridge type filter processed is filtered, and to obtain inorganic polysilazane content be 20.3% relatively uses coating fluid 6.
[comparative example 7]
In the glass of the 5000ml that possesses agitator, thermometer and ingress pipe reaction vessel processed, add dry pyridine 4300g(54.4 mole in nitrogen atmosphere), stir on one side, imported dichlorosilane 545g(5.4 mole with 1 hour from ingress pipe on one side under the temperature of reaction of-40～-30 ℃), the pyridine that generates dichlorosilane adds adult.Imported ammonia 325g(19.1 mole with 1 hour from ingress pipe under the temperature of reaction of-40～-30 ℃), then under-20～-15 ℃, carry out stirring in 2 hours, make to have reacted.After this reaction solution is heated to 25 ℃, filter out the ammonium chloride of generation in nitrogen atmosphere, superfluous ammonia is removed in decompression, then according to ordinary method, solvent is changed to dibutyl ether from pyridinium crosslink, the PTFE that is 0.1 μ m with the filtration diameter in argon gas atmosphere again filter cartridge type filter processed is filtered, and to obtain inorganic polysilazane content be 19.0% relatively uses coating fluid 7.
[comparative example 8]
In comparative example 7, the temperature of reaction of ammonia is changed to-15～-12 ℃ from-40～-30 ℃, then stir 2 hours under-15～-12 ℃, in addition, carry out the operation same with comparative example 7, to obtain inorganic polysilazane content be 19.1% relatively uses coating fluid 8.
[comparative example 9]
In comparative example 7, use dichlorosilane 444g(4.4 mole) with trichlorosilane 13.6g(1.0 mole) mixture replace dichlorosilane 545g(5.4 mole), by ammonia from 325g(19.1 mole) increase to 340g(20.0 mole), in addition, carry out the operation same with comparative example 7, to obtain inorganic polysilazane content be 19.2% relatively uses coating fluid 9.
<analyze: 1h-NMR analyzes>
The silicon dioxide film obtained in embodiment 1～3 is formed with relatively measuring with coating fluid 1～9 of obtaining in coating fluid No.1～3 and comparative example 1～9 1h-NMR.Silicon dioxide film forms being illustrated in Fig. 2～Fig. 4 with coating fluid No.1～No.4. 1in H-NMR spectrum, to more than 4.75ppm and lower than the peak area of the scope of 5.4ppm, be set as A, to more than 4.5ppm and lower than the peak area of the scope of 4.75ppm, be set as B, by more than 4.2ppm and lower than the peak area of the scope of 4.5ppm, being set as C, calculate A/(B+C) value, the value of (A+B)/C.The results are shown in [table 1].
<analyze: GPC >
Form and relatively use coating fluid 1～9 with what obtain in coating fluid No.1～3 and comparative example 1～9 for the silicon dioxide film that obtains in embodiment 1～3, by the result of GPC, calculate respectively the matter average molecular weight of inorganic polysilazane and the content that the matter average molecular weight is the composition below 800.The results are shown in [table 1].Chromatographic column is used the SuperMultiporeHZ-M of TOSOH Co., Ltd. system.
<analysis that inorganic polysilazane is filmed: thickness, IR analyze >
The silicon dioxide film that obtains in embodiment 1～3 is formed by the mode that is relatively 580～620nm with coating fluid 1～9 use spin-coating method according to the thickness that makes dried inorganic polysilazane obtained in coating fluid No.1～3 and comparative example 1～9 and coats on the silicon wafer that diameter that two sides was polished is 4 inches, then under 150 ℃ dry 3 minutes, thereby modulation has the silicon wafer of filming of inorganic polysilazane, measure the thickness, the FT-IR that film.In addition, in FT-IR measures, using silicon wafer that two sides was polished as reference.In addition, thickness is used the F-20 of Filmetrics company system to be measured.The NH/SiH dulling luminosity ratio of being calculated by the result of thickness and FT-IR is shown in [table 1].
[table 1]
[embodiment 4 and comparative example 10]
The silicon wafer that use is used in the analysis of filming of above-mentioned inorganic polysilazane, as burning till of the 1st stage, relative humidity be 90% and the temperature baking oven that is 300 ℃ in burn till 30 minutes, as burning till of the 2nd stage, relative humidity be 10% and the temperature baking oven that is 900 ℃ in burn till 30 minutes, thereby the formation silica insulation film, the thickness of mensuration silicon dioxide film.The thickness of silica insulation film is set as to cure shrinkage (%) with respect to the ratio of the thickness of dried inorganic polysilazane.The results are shown in [table 2].
[table 2]
Silicon dioxide film forms uses coating fluid Cure shrinkage (%)
No.1 16.5
No.2 15.3
No.3 15.1
Relatively use coating fluid
1 18.0
2 17.9
3 18.2
4 19.7
5 20.8
6 18.4
7 17.3
8 17.8
9 16.8
Result from above-mentioned [table 1] and [table 2], contain A/(B+C) the value of value, (A+B)/C and the silicon dioxide film of the of the present invention inorganic polysilazane of matter average molecular weight in specialized range form with coating fluid with contain A/(B+C) value and matter average molecular weight relatively the comparing with coating fluid of the inorganic polysilazane in specialized range not of value, (A+B)/C, cure shrinkage is little, be difficult for to occur silicon dioxide film be full of cracks and with the peeling off of semiconductor substrate.

Claims (5)

1. an inorganic polysilazane, wherein, 1in H-NMR spectrum, to more than 4.75ppm and lower than the peak area of the scope of 5.4ppm, be set as A, to more than 4.5ppm and lower than the peak area of the scope of 4.75ppm, be set as B, when more than 4.2ppm and lower than the peak area of the scope of 4.5ppm, being set as C, A/(B+C) value is 0.9～1.5, (A+B) value of/C is 4.2～50, and the matter average molecular weight obtained according to the polystyrene conversion value is 2000～20000.
2. inorganic polysilazane according to claim 1, wherein, in infrared spectra, at 3300～3450cm -1the maximum absorbance of scope with respect at 2050～2400cm -1the ratio of maximum absorbance of scope be 0.01～0.20.
3. inorganic polysilazane according to claim 1 and 2, it is by after dihalide halosilanes compound, trihalosilane compound or their mixture and alkali reaction being formed add adult, makes this add adult and ammonia react obtains.
4. a silicon dioxide film forms and uses coating fluid, and it contains in claim 1～3 the described inorganic polysilazane of any one and organic solvent as neccessary composition.
5. the formation method of a silicon dioxide film, is characterized in that, silicon dioxide film claimed in claim 4 is formed and coats on matrix with coating fluid, makes this coating fluid and oxidant reaction, thereby form silicon dioxide film.
CN201280020940.6A 2011-06-13 2012-04-09 Inorganic polysilazane, silica film-forming coating liquid containing same, and method for forming silica film Pending CN103502318A (en)

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